Contribution of known endocrine disrupting substances to the estrogenic activity in Tama River water samples from Japan using instrumental analysis and in vitro reporter gene assay

To quantitatively characterize the substances contributing to estrogenic activity in river water, in vitro bioassay using MVLN cells and instrumental analysis using liquid chromatograph–mass spectrometer (LC/MS) or liquid chromatograph–tandem mass spectrometer (LC/MS/MS) were applied to river water extracts taken from various locations in the Tama River, Japan. Tama River water samples were extracted using solid phase extraction and the crude extracts were fractionated by high-performance liquid chromatography (HPLC) into 10 fractions. The sixth fraction contained nonylphenol (NP) and octylphenol (OP) at concentrations in the range of 51.6–147 and 6.9–81.9 ng/L, respectively (concentrations corresponding to the original sample volumes). No estrogenic activity, expressed as 17β-estradiol equivalents (E2-EQ_B), however, was observed in this fraction (<0.6 ng-E2eq/L). Instrumentally determined estrogenic activity (E2-EQ_C), which is the concentrations of NP and OP multiplied by their corresponding relative potency, was below the detection limit of the MVLN cell bioassay. Estrogenic activities were detected only in HPLC fraction nos. 7, 8 and 9. Estrone (E1), estradiol (E2) and bisphenol A (BPA) were detected in these fractions. Estriol (E3) and ethynylestradiol (EE2) were not detected (<0.2 ng/L) in these fractions. The calculated E2-EQ_C for BPA was below the detection limit of bioassay. The E2-EQ_C for E1 and E2 were on the same order as the estrogenic activity determined by the bioassay (E2-EQ_B). The ratios of E2-EQ_C and E2-EQ_B for E1 and E2 in the three factions collectively (nos. 7–9) were 0.49–0.97 and 0.29–1.12, respectively. Above results indicated that the major causal substances to the estrogenic activity in the Tama River were E1 and E2.     

Effect of molding pressure on fabrication of low-crystalline calcite block

We have reported that low-crystalline porous calcite block, which is useful as a bone substitute or a source material to prepare apatite-type bone fillers could be fabricated by exposing calcium hydroxide compact to carbon dioxide gas saturated with water vapor. In the present study, we investigated the effect of molding pressure on the transformation of calcium hydroxide into calcite and the mechanical strength of the carbonated compact. Transformation into calcite was almost completed within 72 h, however, a small amount of Ca(OH)₂ still remained unreacted at higher molding pressure because of incomplete penetration of CO₂ gas into the interparticle space due to dense packing of Ca(OH)₂ particles. On the other hand, high molding pressure resulted in an increase in diametral tensile strength (DTS) of the calcite compact formed. Critical porosity of the calcite block was calculated as approximately 68%.     

Controlled nanoporous structures of a marine diatom

We demonstrated chemical etching of a marine diatom shell with 1 N NaOH for controlling the pore size of nanoporous structures of the shell under various conditions. Scanning electron microscopy (SEM) images clearly revealed that the pore size of the diatom shells was regulated in the case of etching at 25 degrees C. In contrast, fluctuations in the etched structures was relatively high even during short periods degradation at 40, 60, and 90 degrees C; therefore, controlled nanoporous structures could not be fabricated. This is the first example of artificial modification of natural diatom shells at the nanoscale although diatom shells have been widely used in industry. In addition, a backbone-like structure was observed during the etching process. The structure was similar to the intermediate structure observed during the primitive stage of the diatom cell growth. Probably, this information is valuable for studying the mechanism of nanoporous structures of diatoms.     

Solubility of propylene in semicrystalline polypropylene

Gas solubilities and polymer swelling in propylene and semicrystalline polypropylene system at temperatures of 323.2 and 348.2 K and pressures up to propylene's vapor pressure were measured. Pressure, specific volume, and temperature (PVT) measurements of polypropylene were carried out at temperatures from 313 to 573 K and pressures up 200 MPa. Two kinds of polypropylenes, which had different stereoregularities, were used for both solubility and PVT measurements. The solubilities were correlated with the Sanchez–Lacombe equation of state (EOS) with temperature‐dependent binary interaction parameters to within 5% average relative percentage deviation. Swelling ratios estimated with Sanchez–Lacombe EOS coupled with optimized interaction parameters were 20% lower than the experimental values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1134–1143, 2001     

Gelation of poly(vinyl alcohol)/water/dimethylformamide solutions and properties of dried films

The properties of solutions for syndiotacticity-rich poly(vinyl alcohol) (s-PVA)/dimethylformamide (DMF)/water systems, the gelation of the s-PVA solutions, and the properties of the dried s-PVA gel films were examined. From the results of the dissolution temperature of the polymer, the gelation temperature of the solutions, the melting temperature of the gels, and the compressive modulus of the gels, the solubility of the polymer was the highest at DMF contents of 10–20 vol %. The maximum dynamic tensile modulus of the drawn (×18) films obtained from the dried gel films with a DMF content of 10 vol % was 54.9 GPa at 20°C. The orientation of the polymer chains in the amorphous regions was higher than that in the crystalline regions. The orientation of the polymer chains in the amorphous regions for the drawn films with a DMF content of 10 vol % was higher than that for the drawn films with a DMF content of 60 vol %. The orientation of the polymer chains in the amorphous regions was considered to play an important role in the properties of high strength and high modulus. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1661–1667, 1998     

Linked‐BINOL: An Approach towards Practical Asymmetric Multifunctional Catalysis

The development and application of a novel linked‐1,1′‐binaphthol (linked‐BINOL) as an approach towards practical asymmetric multifunctional catalysis is described. Linked‐BINOL was first designed to increase the stability of a Ga‐Li‐BINOL complex against ligand exchange with 4‐methoxyphenol. An oxygen‐containing linked‐BINOL, which is a semi crown ether, was effective in both promoting the formation of a monomer complex and increasing the stability of the Ga‐Li complex. A Ga‐Li‐linked‐BINOL complex promoted the epoxide opening reaction in up to 96% enantiomeric excess (ee). Second, based on the X‐ray structural information of the Ga‐Li‐linked‐BINOL complex, we designed a more stable lanthanide linked‐BINOL complex. An air‐stable, storable, and reusable La‐linked‐BINOL complex promoted the Michael reaction in up to >99% ee. The catalyst activity remained unchanged after storage under air for 4 weeks. Calculations suggested that the linked‐BINOL would function as a pentadentate ligand in a lanthanum complex, thus efficiently improving the stability of the complex. Finally, the linked‐BINOL was applied to a new homobimetallic multifunctional catalysis. A dinuclear Zn‐Zn‐linked‐BINOL complex promoted the enantio‐ and diastereoselective direct aldol reaction in up to 99% ee, where one Zn cation might function as a Lewis acid and the other Zn‐phenoxide as a Brønsted base.     

Measurement of electric intensity distribution inside human cadaver cochlea for multichannel cochlear implants

We have proposed a Tripolar Electrode Stimulation Method (TESM) which may succeed in narrowing the stimulation region and continuously moving the stimulation site for cochlear implants. The TESM stimulates the auditory nerve array through lymphatic fluid by means of three adjacent electrodes selected from among an electrode array. Currents are emitted from the electrodes on each side and the central electrode receives them. The current received by the latter electrode is equal to the sum of the currents emitted from the electrodes on the two sides. In this paper, the electric intensity profiles produced by the TESM and by monopolar stimulation were measured in a human cadaver cochlea and in a saline solution. We found that in the TESM, the electric intensity profile produced in the human cadaver cochlea was about the same as that in the saline solution. In addition, in the TESM, the electric intensity profile was much sharper than that of monopolar stimulation in the human cadaver cochlea. Furthermore, the nervous excitation region could be localized in a certain range by means of TESM. © 1999 Scripta Technica, Electr Eng Jpn, 129(1): 1–9, 1999     

Color gamut mapping based on a perceptual image difference measure

Gamut mapping is a color transformation technique to solve a problem caused by mismatch of gamuts among imaging devices. One plausible goal of gamut mapping is to find a reproduction that is perceptually closest to the corresponding original image when an exact color matching is not possible. Several measures to quantify the perceptual difference between images have been proposed and applied to the gamut mapping problem. However most of the measures, such as average color difference, are applied on a pixel‐wise basis and show poor correlation with human visual perception. This article describes a model of the perceptual image difference for a given pair of images, which takes the human's contrast sensitivity into account and applies the model to a gamut mapping for generating a reproduction with minimum perceptual image difference. The model has a multispatial‐frequency channel structure with tunable peak gains for each channel, which are determined by psychophysical experiments, so that the model output fits the observer's sensitivity to the image difference. A gamut‐mapped image with minimum perceptual image difference is obtained by an iterative minimization process. To evaluate the proposed method, subjective evaluation experiments are performed to construct ratio scales that measure perceptual image difference of gamut‐mapped reproductions generated by the proposed and pixel‐wise methods. Results show that the reproductions by the proposed method are perceived as perceptually closest to the original, and the model's estimate of perceptual difference correlates better with the experimentally measured perceived image difference than other pixel‐wise measures. © 1999 John Wiley & Sons, Inc. Col Res Appl, 24, 280–291, 1999     

Morphology and physical-chemical properties of baked nanoporous frustules

We investigated the morphology and physical-chemical properties of baked and unbaked nanoporous frustules. Scanning electron microscopy (SEM) observations showed that the nanoporous structures of frustules unchanged at 400 degrees C even after baking for 6 h. During baking at 800 degrees C, the frustule structures changed dramatically. On the other hand, Fourier transform infrared spectroscopy (FTIR) of bulk frustule samples indicated that physical-chemical properties of the frustules had clearly changed after baking at not only 800 degrees C but also 400 degrees C. These results showed that the reconstruction of the structures had occurred inside the frustules, even though the morphology of the frustules had not apparently changed at 400 degrees C. In order to characterize the exact shape of the frustules, living diatom cells were grown on a functionalized mica surface, and then baked without any chemical treatment for SEM study. This 'direct baking' technique is effective for comparing minute structures of the frustules, because completed combination of every part of the frustules can be observed.     

Experimental characterization of high-speed impact damage behavior in a three-dimensionally woven SiC/SiC composite

This paper discusses high-speed impact damage in a three-dimensionally woven SiC/SiC composite (3D-CMC). The impact damage was introduced by a steel ball projectile in 3D-CMC plates with and without thermal exposure. The surface and internal damages were observed by optical microscopy and X-ray CT. A crater was observed on the collision surface. The X-ray CT measurement revealed that multiple pyramid-shaped cone cracks were generated beneath the crater when the impact speed was relatively low. At an impact speed exceeding the critical speed, a spall fragment was ejected from the back surface, while no internal damage was observed in the fragment. The spall fracture mode differed between the virgin and the thermally-exposed specimens. This difference is the result of embrittlement of the fiber/matrix interface due to oxidation of the carbon coating layer in the thermally-exposed specimen. In addition, it is found that z-yarns improve impact resistance by constraining delamination.